Solid Base Catalyst For Transesterification Research Articles

Potassium supported on zeolite-geopolymer hybrid materials as a new solid base catalyst for transesterification of soybean oil

The heterogeneous base catalysts were developed from zeolite-geopolymer hybrid material (Zeo-Geo) as a new support for potassium in transesterification of soybean oil. Zeo-Geo was prepared by mixing Al metal, metakaolin, and fumed silica in NaOH solution and curing at 60 °C, 24 h and 110 °C, 12 h. The Zeo-Geo contained a mixed phase of geopolymer and X-type zeolite. The xK/Zeo-Geo with x = 5, 10 or 15 wt% potassium were prepared by impregnation of Zeo-Geo with potassium acetate followed by calcination at 400 °C for 3 h. The phases of potassium were mainly K2O and K2CO3 and the basicity increased with potassium loading. The 15K/Zeo-Geo was the most active catalyst in transesterification of soybean oil with methanol, at 70 °C providing 97.64% biodiesel yield under the optimum condition: reaction time = 3 h, methanol to oil molar ratio = 16:1 and catalyst amount = 2 wt%. The catalyst was reused in 5 cycles without a significant activity loss and leaching of active species. From this study, 15K/Zeo-Geo has a potential for further development in large-scale production.

Application of dolomite as solid base catalyst for transesterification of rapeseed oil with butanol

The article presents the results of studies on the transesterification of rapeseed oil with butanol using a heterogeneous catalyst (0.315–0.1 mm) of the dolomite calcined at 850 °C. Experimental plan was prepared and results analyzed using response surface methodology. Interaction of four independent variables were analyzed and presented in the article. It was found that the biggest influence on ester yield have the temperature and the duration of the reaction. After optimizing the process, it was found that in 8 h the highest ester yield of 94.55 wt% is obtained using 5.24 wt% of dolomite, at 110 °C and 13.71:1 M ratio of butanol to oil.

Layered double hydroxide uniformly coated on mesoporous silica with tunable morphorlogies for catalytic transesterification of glycerol with dimethyl carbonate

Layered double hydroxides (LDH) is an attractive solid base catalyst for transesterification of glycerol with dimethyl carbonate. A major challenge in enhancing the catalytic performance of LDH for this process is to overcome the internal diffusion limitations and increase the availability of basic sites. Herein we present ultrasonic and hydrothermal post-synthesis strategies in uniformly coating of LDH on mesochannels of mesoporous silica. The effects of precursors, preparation methods and morphologies on preparing LDH/SBA-15 nano-composites were investigated. Rice-shaped LDH/SBA-15 nano-composite catalysts exhibited better performance with a 78% glycerol conversion and 90% selectivity of glycerol carbonate than the catalysts with morphologies of short-rods, and long-rods. The results revealed that hierarchical nanostairs at the edge and well-ordered mesochannels stacked along the long axis direction reduced internal diffusion path lengths and increased availability of basic sites. This approach in morphology controlling synthesis of LDH based nano-composite catalysts shed light on the uniformly coating of other diatomic and triatomic metal LDH within mesochannels of mesoporous silica to fabricate novel nano-composite catalysts.

Design of nitrogen-doped graphitized 2D hierarchical porous carbons as efficient solid base catalysts for transesterification to biodiesel

2D graphitized porous carbons decorated with high contents of nitrogen sites such as pyridinic nitrogen were developed, which were used as efficient and reusable solid base catalysts for transesterification to biodiesel.

Transesterification of non-edible oils over potassium acetate impregnated CaO solid base catalyst

Biodiesel production through transesterification reaction with methanol using calcium oxide (CaO) as a solid base catalyst is restricted due to the need to the high molar ratio of methanol to oil and long reaction time. Therefore, the CaO catalyst was modified by potassium acetate (PA) to prepare PA/CaO solid base catalyst via wet impregnation method. X-ray Diffraction, Scanning Electron Microscopy, Thermal Gravimetric Analysis, Fourier Transform Infra-Red spectroscopy, Hammett indicator (basic strength), and the Inductive Couple Plasma techniques, were applied to characterize the prepared catalyst. The effect of the PA ratio loaded on CaO and calcination temperature were investigated as well. The catalyst activity was tested through transesterifcation reaction of non-edible oils, namely bitter almond oil BAO and waste fish oil WFO, with methanol. Transesterifcation process was optimized through the parameters involving the solid catalyst amount, methanol to oil molar ratio, reaction temperature, and reaction time. The highest methyl ester yield from both BAO (91.22 wt%) and WFO (93.30 wt%) were achieved by employing 2.0 wt% , and 1.0 wt% of PA/CaO catalyst, respectively, 9:1 methanol to oil molar ratio, 60 °C reaction temperature, and 120 min reaction time. The prepared catalyst was retrievable and thermally stable giving a yield up to 75 wt% after a 4th cycle reuse. The fuel properties of the raw oils were significantly enhanced as a result of transesterification, and were in conformity with the ASTM D 6751 limits. Conversion of the non-edible oils to biodiesel using the catalyst was confirmed by 1H NMR spectroscopy which gives yield percent close to those of the practically obtained. Moreover, the FTIR spectroscopy assured the conversion of the non-edible oils into biodiesel. As such, PA/CaO composite may be considered as a promising solid base catalyst for transesterification of non-edible oils with methanol.

Optimization of methyl esters production from non-edible oils using activated carbon supported potassium hydroxide as a solid base catalyst

The present investigation reports transesterification of non-edible oils, waste cooking oil (WCO) and waste fish oil (WFO) with methanol using activated carbon supported potassium hydroxide (KOH) as a solid base catalyst. Activated carbon was prepared from polyethylene terephthalate waste and loaded with KOH by wet impregnation method to prepare KOH/AC solid base catalyst. X-ray diffraction and Scanning Electron Microscopy (SEM) were utilized to characterize the resulting solid base catalyst. Retention method was utilized to measure the specific surface area of the activated carbon and its derived solid base catalyst, while Hammett indicator method was followed to determine the basic strength of the prepared solid base catalyst. The prepared catalyst has granular and porous structures with a high basicity and a superior catalytic performance for the transesterification reaction. Transesterification reaction variables were arranged to obtain the best biodiesel yield. The highest methyl ester yield from WCO (88.12% w/w with an ester content of 96.68% w/w) was obtained by employing 3.5 wt.% KOH/AC catalyst, 9:1 methanol to oil molar ratio, 65 °C reaction temperature, the reaction time of 180 min and the stirring rate of 600 rpm, while maximum methyl ester yield from WFO (92.66% w/w with 96.98% w/w ester content) was produced with 3.0 wt.% KOH/AC catalyst, 9:1 methanol to oil molar ratio at 65 °C for 150 minutes of the reaction and 600 rpm. The prepared solid base catalyst was recoverable and thermally stable giving a yield of 70 wt.% after the 5th cycle. The fuel properties of the raw oils were significantly enhanced after transesterification with methanol in the presence of KOH/AC, and were in conformity with the ASTM D 6751 limits as well. Therefore, the prepared KOH/AC composite may be considered as a promising solid base catalyst for transesterification of non-edible oils with methanol.

Hydrogel-Templated Solid Base Catalysts for Transesterification of Soybean Oil.

A new method for utilization of hydrogel is proposed here for the preparation of solid base catalysts for the transesterification of vegetable oil. When a solution of KF is mixed with a solution of Ca(NO3)2, CaF2 is obtained and inactive as a catalyst in the transesterification of vegetable oils. The catalysts were synthesized by the sequential incorporation of KF and/or Ca(NO3)2 solutions into the hydrogel upon microwave irradiation and then the as-obtained hydrogel was calcined at 800°C for 5 hours to eliminate the template and yield catalysts for the biodiesel productions. The prepared catalysts obtained by the different ways in the incorporation of ions into the hydrogel showed different physical properties and catalytic activities in the transesterification of soybean oil. All catalysts, except the low concentration of Ca(NO3)2, exhibiting the high activity yielding more than 90% FAME after 1 hour at 65°C, using oil to methanol molar ratio of 1:15 and 10 wt% of catalyst amounts.

Investigation of boiler scale deposits as heterogeneous base catalyst for biodiesel production from jatropha oil

ABSTRACTExploitation of non-edible oils, especially jatropha oil, for biodiesel production has been investigated extensively due to its high oil content. In this study, boiler scale deposits (BSD), an industrial waste, was calcined at 1000°C in a muffle furnace and investigated as a heterogeneous solid base catalyst for transesterification of jatropha oil to produce biodiesel. The physicochemical properties of the calcined BSD catalyst were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). Due to high free fatty acid (FFA) content of oil, a two-stage process, viz., acid catalyzed esterification pretreatment followed by transesterification, was employed for biodiesel production. Esterification was conducted under the following conditions: 2% (v/v) H2SO4, methanol to oil molar ratio 6:1, reaction time 2 h and reaction temperature 60°C and the acid value was reduced to 3.65 mg of KOH/g. Process parameters for the transesterification were 8% (w/w) catalyst,12:1 methanol to oil molar ratio, 3 h reaction time and 65°C reaction temperature and biodiesel conversion of 82.85% was reported. The biodiesel conversion was characterized by 1H nuclear magnetic resonance spectroscopy (1H-NMR).

Sodium Titanate Nanotubes as Efficient Solid Base Catalysts for Transesterification of Cyclic Carbonates

Sodium Titanate Nanotubes as Efficient Solid Base Catalysts for Transesterification of Cyclic Carbonates

3-69 大豆油のエステル交換反応に対する各種固体塩基の触媒活性((18)BDF1,Session 3 バイオマス等,研究発表(口頭発表))

3-69 大豆油のエステル交換反応に対する各種固体塩基の触媒活性((18)BDF1,Session 3 バイオマス等,研究発表(口頭発表))

Enhanced biodiesel production from Jatropha oil using calcined waste animal bones as catalyst

This study is focused on the investigation of animal bones modified with potassium hydroxide (KOH) as heterogeneous solid base catalyst for transesterification of non-edible Jatropha oil. The prepared catalyst was characterized by energy dispersive X-ray (EDX) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermo-gravimetric analysis (TGA). The prepared catalyst had a high catalytic activity for transesterification. In addition, the catalyst had excellent stability, there by having potential use as a heterogeneous catalyst for biodiesel production from Jatropha oil with a high free fatty acid (FFA) yield. The experimental results revealed the optimal parametric conditions viz. methanol/oil molar ratio, 9:1, calcination temperature, 900 °C and catalyst concentration, 6.0 wt % of oil corresponding to a maximum fatty acid methyl esters (FAME) yield of 96.1% at temperature of 70 ± 3 °C in reaction time of 3 h. Reusability results of the prepared catalyst confirmed that it could be reutilized up to 4 times without losing much activity, thus giving birth to a potentially applicable possibility in biodiesel production.

A novel solid base catalyst for transesterification of triglycerides toward biodiesel production: Carbon nanohorn dispersed with calcium ferrite

Carbon nanohorn (CNH) dispersed with a calcium ferrite Ca2Fe2O5 (Ca2Fe2O5–CNH) was synthesized as a new catalyst, and its superior catalytic activity to convert a triglyceride to a fatty acid methyl ester via transesterification reaction was demonstrated. The process to prepare this catalyst has three steps as follows. For the first step, Fe-dispersed CNH (Fe-CNH) was synthesized by a gas-injected arc-in-water method. For the second step, the oxidation treatment in diluted CO2 or in air was performed on Fe-CNH to transform Fe nanoparticles dispersed in Fe-CNH to Fe3O4 or Fe2O3, respectively. For third step, Fe3O4-dispersed CNH (Fe3O4-CNH) or Fe2O3-dispersed CNH (Fe2O3-CNH) was co-calcined with Ca(NO3)2, resulting to the formation of Ca2Fe2O5–CNH. The powdery catalysts of Ca2Fe2O5–CNH can be recovered by magnetic field for recycled use. In the transesterification experiment, tricaprylin was converted to methyl caprylate. The reaction rate of this transesterification using Ca2Fe2O5–CNH catalysts was obviously higher than using conventional CaO catalyst. Also CNH supporting CaO without including Fe (CaO-CNH) was prepared, and this catalyst exhibited a high catalytic activity for this transesterification. However, CaO-CNH did not have the property for magnetic recovery. Among the catalysts prepared here, Ca2Fe2O5–CNH prepared using Fe3O4-CNH as precursor exhibited the highest reaction rate for the transesterification. The hybridization of the calcium ferrite possessing basic sites with hydrophobic CNH was considered to be the key factor for its high catalytic performance.

Influence of green catalyst on transesterification process using ultrasonic-assisted

Expansion of biodiesel production through transesterification reaction is restricted on the highly corrosive catalyst that generates environmental pollution. An exploration towards an environment-friendly and cleaner catalyst using biomass waste has become an attractive research in recent years. The aim of this study is to investigate empty fruit bunch doped with potassium hydroxide as a heterogeneous solid base catalyst for transesterification of rubber seed oil with methanol in ultrasonic batch system. Catalyst preparation was done using incipient wetness impregnation method. Synthesised catalyst named empty fruit bunch-potassium hydroxide was characterised by Fourier Transform Infrared, X-ray Diffraction and Brunauer–Emmett–Teller. Maximum free fatty acid reduction of 97.6% via esterification in mechanical stirring reactor was attained using 2.5 wt. % sulphuric acid and 12:1 methanol to oil molar ratio at 65 °C for 50 min. In the case of transesterification, saponification was formed under operating conditions of 15 wt. % of synthesised catalyst and 15:1 methanol to oil molar ratio at 40 °C for 30 min. This study indicated that empty fruit bunch-potassium hydroxide as the catalyst in transesterification reaction was ineffectiveness when assisted by ultrasonic.

Biodiesel production from non-edible Silybum marianum oil using heterogeneous solid base catalyst under ultrasonication

The aim of this study is to investigate modified TiO2 doped with C4H4O6HK as heterogeneous solid base catalyst for transesterification of non-edible, Silybum marianum oil to biodiesel using methanol under ultrasonication. Upon screening the catalytic performance of modified TiO2 doped with different K-compounds, 0.7 C4H4O6HK doped on TiO2 was selected. The preparation of the catalyst was done using incipient wetness impregnation method. Having doped modified TiO2 with C4H4O6HK, followed by impregnation, drying and calcination at 600°C for 6h, the catalyst was characterized by XRD, FTIR, SEM, BET, TGA, UV and the Hammett indicators. The yield of the biodiesel was proportional to the catalyst basicity. The catalyst had granular and porous structures with high basicity and superior performance. Combined conditions of 16:1 molar ratio of methanol to oil, 5 wt.% catalyst amount, 60°C reaction temperature and 30min reaction time was enough for maximum yield of 90.1%. The catalyst maintained sustained activity after five cycles of use. The oxidative stability which was the main problem of the biodiesel was improved from 2.0h to 3.2h after 30days using ascorbic acid as antioxidant. The other properties including the flash point, cetane number and the cold flow ones were however, comparable to international standards. The study indicated that Ti-0.7-600-6 is an efficient, economical and environmentally, friendly catalyst under ultrasonication for producing biodiesel from S. marianum oil with a substantial yield.

Application of zirconia modified with KOH as heterogeneous solid base catalyst to new non-edible oil for biodiesel

This study seeks to investigate zirconia modified with KOH as heterogeneous solid base catalyst for transesterification of new non-edible, Silybum marianum (oil content 46%, FFA 0.68% and linoleic acid 65.68%) oil using methanol to biodiesel. Having screened the catalytic performance of ZrO2 loaded with different K-compounds, 32% KOH loaded on ZrO2 was chosen. The catalyst was prepared using incipient wetness impregnation method. Following drying (after impregnation) and calcination at 530°C for 5h, the catalyst was characterized by means of Hammett indicators, XRD, FTIR, SEM, TGA and N2 adsorption desorption measurements. It was found that the yield of the fatty acid methyl esters (FAME) was related to the catalyst base strength. The catalyst had granular and porous structures with high basicity and superior catalytic performance for the transesterification reaction. Maximum yield (90.8%) was obtained at 15:1 methanol to oil molar ratio, 6% catalyst amount, 60°C reaction temperature in 2h. The catalyst maintained sustained activity after five times of usage. The oxidative stability and iodine value were the only unsuitable properties of the biodiesel (out of range) but can easily be improved. The cetane number, flash point and the cold flow properties among others were however, comparable to international standards. The study indicated that KOH(32%)/ZrO2-5 is an economically, suitable catalyst for producing biodiesel from S. marianum oil which is a potential new non-edible feedstock that can contribute positively to biodiesel industry as its biodiesel can be rated as promising alternate fuel.

Catalytic synthesis of biodiesel from pongamia glabra over zirconia and its modified forms

Zirconia & its modified forms such as Mo(VI)/ZrO2, Pt-SO42−/ZrO2, MgO & MgO-ZrO2 mixed oxide were prepared by impregnation method. These catalysts were analyzed for surface acidity, surface basicity and crystallinity by using techniques such as TPD & powder X-ray diffraction. Mo(VI)/ZrO2, Pt-SO42−/ZrO2 were used as solid acid catalysts for esterification of pongamia glabra (karanja) oil to reduce the concentration of free fatty acid and MgO and MgO-ZrO2 mixed oxide were used as solid base catalysts for transesterification of karanja oil to produce biodiesel. These zirconia catalysts were found to be highly efficient for the synthesis of biodiesel with more than 90% yield of biodiesel. These solid catalysts can be effectively reactivated and reused.

Purification to remove leached CaO catalyst from biodiesel with the help of cation-exchange resin

Many researchers focused their attentions on calcium oxide (CaO) as a solid base catalyst for transesterification of vegetable oil with methanol, but, a small amount of soluble substance is leached away from CaO catalyst under the reacting condition. In the present research work, purification of biodiesel contaminated with the leached CaO catalyst was studied. Biodiesel was prepared by the CaO-catalyzed transesterification of waste cooking oil, and calcium content of the prepared biodiesel was 200ppm. The purifying test to remove the leached CaO catalyst was carried out by passing the prepared biodiesel through a column packed with cation-exchange resin. Among the employed four resins differing in the polymer matrix, the acidic functional group and the counter-cation, the protonated resins consisting of macro-reticular polymer matrix resulted in the high removal efficiency. Then, an influence of the internal mass transfer on the removal efficiency was investigated on the basis of data collected by purifying the biodiesel–methanol mixture. The addition of methanol promoted internal mass transfer, so that the 100% removal of the leached CaO catalyst was achieved successively. Furthermore, reduction of the free glycerol was examined for the resin-purification.

Preparation of biodiesel catalysed by KF/CaO with ultrasound

Biodiesel, chemically consists of fatty acid methyl ester (FAME) produced by methanolysis of natural triglycerides, such as animal fats and vegetable oils, is a kind of biomass energy, which is renewable and ecofriendly. In this article, KF/CaO was used as solid base catalyst for transesterification of soya bean oil and methanol, while ultrasound as supplementary means. Compared to mechanical stirring, ultrasound treatment is an effective method to increase the yield of FAME and shorten reaction time. By single-factor method, the optimisation of reaction conditions has been studied. The research showed that the optimum reaction conditions were: w(catalyst)/w(oil): 3%, reaction temperature: 65°C, n(methanol)/n(oil): 12, reaction time: 1 h, sound intensity: 1.01 W cm−2, frequency: 20 kHz, the yield of FAME could be 97%.

Hydrotalcite-like compounds containing transition metals as solid base catalysts for transesterification

Hydrotalcite-like compounds (HTLCs) containing Mg 2+, Ni 2+ and Al 3+ layered double hydroxide (LDH) were synthesized by co-precipitation method and calcined at 773 K for 10 h performed as heterogeneous base catalysts for transesterification of soybean oil with methanol to produce biodiesel. These four different MgAlNi catalysts were characterized by nitrogen physisorption, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), temperature programmed desorption with CO 2 (CO 2-TPD), nitrogen adsorption–desorption. The Mg/Ni molar ratio varies over the range from 4 to 16 of the MgAlNi catalysts at a constant Al ratio in the hydrotalcite-like structures. The conversion of FAME was related to the basicity and Mg content of the MgAlNi catalysts, with MgAlNi 16 showing the highest basicity, and the lowest surface area due to Mg 2+–O 2− and Al 3+–O 2− pairs. The optimum conditions were obtained with a methanol/oil molar ratio of 21, 0.3% catalyst (w/w, oil), and 1200 rpm stirring speed for 4 h at 338 K, which results in the highest FAME conversion of 87%.

One-pot synthesis of calcium-incorporated MCM-41 as a solid base catalyst for transesterification of palm olein

Direct generation of basic sites on mesoporous silica MCM-41 through calcium incorporation was achieved via a one-pot synthesis. The effect of calcium salt precursors was addressed in terms of structure, morphology, and basic property. The catalysts were evaluated for potential application in transesterification of palm olein with methanol to produce biodiesel. Among all of the catalysts tested in this study, the most efficient calcium-incorporated MCM-41 was derived from CaO precursor, affording over 90 wt.% of fatty acid methyl ester after 3 h of reaction at 200 °C. ► Calcium-incorporated MCM-41 catalysts were prepared via a one-pot synthesis. ► The catalysts possess ordered mesopores with high surface area. ► The basicity of the catalysts was higher than that of siliceous MCM-41. ► The Ca/MCM-41 catalysts were active for transesterification of vegetable oil. ► The catalysts yielded over 90% biodiesel product.